Synergistically active herbicidal mixtures

ABSTRACT

A composition which comprises  
     a) at least one sulfonylurea of the formula I  
                 
 
      wherein the radicals R 1  to R 5  and the index n are as defined in the specification, or an environmentally compatible salt of the sulfonylurea, and  
     b) at least one herbicidal compound selected from groups b 1  to b 41  as defined in the specification, or an environmentally compatible salt of the herbicidal compound,  
     and which exhibits a synergistic herbicidal effect.

[0001] The present invention relates to a synergistically activeherbicidal mixture composed of a sulfonylurea derivative (a) of theformula I and one or more herbicidal compounds b1 to b41.

[0002] Herbicidally active sulfonylureas of the formula I have beendisclosed in the prior art, for example in EP-388 873, EP-559 814,EP-291 851 and DE-40 07 683 and the Conference Proceedings “Fluorine inAgriculture”, Jan. 9-11 1995, Manchester, chapter “New FluoroIntermediates for Herbicidal Sulfonylureas”.

[0003] Herbicidal compounds b1 to b41 are described, for example, in“Herbizide”, Hock, Fedtke, Schmidt, 1st Edition, Thieme 1995 (see“quinclorac” p. 238, “molinate” p. 32, “butachlor” p. 32, “pretilachlor”p. 32, “dithiopyr” p. 32, “mefenacet” p. 32, “fenoxapropethyl” p. 216,“dimepiperate” p. 32, “pyrazolate” p. 146, “pyrazoxyfen” p. 146,“bensulfuron-methyl p. 31, “pyrazosulfuron-ethyl” p. 31, “cinosulfuron”p. 31, “benfuresate” p. 233, “bromobutide” p. 243, “dymrone” p. 243,“dimethyametryn” p. 118, “esprocarb” p. 229, “pyributicarb” p. 32,“cinemthylin” p. 32, “propanil” p. 32, “2,4-D” p. 30, “bentazone” p. 30,“DPX-A-8947” p. 175, “mecoprop-P” p. 237, “chlorpropham” p. 205,“thiocarbazil” p. 229, “ethoxyfen” p. 30, “haloxyfop-P-methyl” p. 38,“haloxyfop-ethoxyethyl” p. 38, “flumiclorac-pentyl” p. 35, “flupropacil”p. 143, “nipyraclofen” p. 145, “metosulam” p. 33,“ethametsulfuron-methyl” p. 36, “thifensulfuron-methyl” p. 35 or in“Agricultural Chemicals”, Book II Herbicides, 1993 see “thiobencarb” p.85, “benzofenap” p. 221, Inapropanilid” p. 49, “piperophos” p. 102,“anilofos” p. 241, “TH-913” p. 150, “HW-52” p. 54, “ICIA-0051” p. 268,“poast” p. 253, “focus” p. 222, “dimethenamid” p. 48, “sulfosate” p.236, “2,4-DB” p. 10, “dichlorprop-P” p. 6, “flupoxam” p. 44,“prosulfocarb” p. 84, “quinmerac” p. 233, “metazachlorn” p. 64,“flurtamone” p. 265, “bromofenoxim” p. 228, “fomesafen” p. 248,“imazethabenz-methyl” p. 153, “clodinafop” p. 214, “fenoxaprop-P-ethyl”p. 208, “fluazifop-P-butyl” p. 207, “quizalofop-P-ethyl” p. 210,“quizalofop-terfuryl” p. 211, “flumioxazin” p. 43, “flumipropyn” p. 267,“sulfentrazone” p. 261, “thiazopyr” p. 226, “pyrithiobac-sodium” p. 266,“flumetsulam” p. 227, “amidosulfuron” p. 151, “halosulfuron-methyl” p.148, “rimsulfuron” p. 138, “tribenuron-methyl” p. 139,“triflusulfuron-methyl” p. 137, “primisulfuron” p. 147 or in “ShortReview of Herbicides & PGRs 1991, Hodogaya Chemicals see “furyloxyfen”p. 142, “triazofenamid” p. 268, “KH-218” p. 52, “NSK-850” p. 52,“JC-940” p.90, “AC-92553” p. 58, “buthidazole” p. 88, “cyprazole” p.38,“allidochlor” p. 48, “benzoylprop-ethyl” 5 p. 38, “chlorthiamid” p. 150,“diphenamid” p. 34, “flamprop-methyl” p. 40, “fosamin” p. 232,“isoxaben” p. 42, “monalide” p. 32, “naptalam” p. 36, “pronamid” p. 34,“bialaphos” p. 234, “glufosinate-ammonium” p. 234, “glyphosaten p.” 232,“aamitrol” p. 254, “clomeprop” p. 20, “dichlorprop” p. 6, “fenoprop” p.8, “fluroxypyr” p. 156, “MCPA” p. 4, “MCPB” p. 8, “mecoprop” p. 6,“napropamide” p. 16, “triclopyr” p. 154, “chloramben” p. 28, “dicamba”p. 26, “clomazone” p. 268, “diflufenican” p. 42, “fluorochloridone” p.266, “fluridone” p. 156, “asulam” p. 112, “barban” p. 100, “butylate” p.106, “carbetamide” p. 36, “chlorobufam” p. 100, “cycloate” p. 108,“desmedipham” p. 104, “di-allate” p. 106, “EPTC” p. 108, “orbencarb” p.112, “pebulate” p. 106, “phenisopham” p. 118, “pendimedipham” p. 104,“propham” p. 100, “sulf-allate” p. 110, “terbucarb” p. 102, “tri-allate”p. 108, “vernolate” p. 108, “acetochlor” p. 48, “alachlor” p. 46,“diethathyl-ethyl” p. 48, “dimethachlor” p. 50, “metolachlor” p. 46,“propachlor” p. 44, “pyrnachlor” p. 44, “terbuchlor” p. 48, “xylachlor”p. 52, “alloxydim” p. 260, “clethodim” p. 270, “cloproxydimo p. 268,“tralkoxydim” p. 270, “dalapon” p. 212, “ethofumesate” p. 124, “benefin”p. 54, “butralin” p. 58, “dinitramin” p. 56, “ethalfluralin” p. 60,“fluchloralin” p. 54, “isopropalin” p. 58, “nitralin” p. 58, “oryzalin”p. 60, “prodiamine” p. 62, “profluralin” p. 54, “trifluralin” p. 54,“dinoseb” p. 128, “dinoseb-acetate” p. 128, “dinoterb” p. 128, “DNOC” p.126, “acilfluorfen-sodium” p. 142, “aclonifen” p. 146, “bifenox” p. 140,“chlornitrofen” p. 138, “difenoxuron” p. 76, “fluorodifen” p. 138,“fluoroglycofen-ethyl” p. 146, “lactofen” p. 144, “nitrofen” p. 136,“nitrofluorfen” p. 140, “oxyfluorfen” p. 140, “cyperquat” p. 158,“difenzoquat” p. 160, “diquat” p. 158, “paraquat” p. 158,“benzthiazuron” p. 82, “buturon” p. 66, “chlorbromuron” p. 72,“chloroxuron” p. 76, “chlortoluron” p. 74, “cycluron” p. 84, “dimeturon”p. 88, “diuron” p. 70, “ethidimuron” p. 86, “fenuron” p. 64,“fluometuron” p. 68, “isoproturon” p. 80, “isouron” p. 88, “karbutilate”p. 76, “linuron” p. 72, “methabenzthiazuron” p. 82, “metoxuron” p. 72,“monolinuron” p. 66, “monuron” p. 64, “neburon” p. 72, “siduron” p. 68,“tebuthiuron” p. 86, “trimeturon” p. 64, “isocarbamid” p. 168,“imazamethapyr” p. 172, “imazapyr” p. 170, “imazaquin” p. 170,“imazethapyr” p. 172, “methazole” p. 162, “oxadiazon” p. 162,“tridiphane” p. 266, “bromoxynil” p. 148, “ioxynil” p. 148,“diclofop-methyl” p. 16, “fenthiaprop-ethyl” p. 20, “fluazifop-butyl” p.18, “haloxyfop-methyl” p. 18, “isoxapyrifop” p. 22, “propaquizafop” p.24, “quizalofop-ethyl” p. 20, “chlorfenac” p. 258,“chlorophenprop-methyl” p. 258, “chloridazon” p. 174, “maleic hydrazide”p. 162, “norflurazon” p. 174, “pyridate” p. 176, “clopyralid” p. 154,“picloram” p. 154, “chlorimuron-ethyl” p. 92, “chlorsulfuron” p. 92,“flazasulfuron” p. 96, “metsulfuron-methyl” p. 92, “nicosulfuron” p. 96,“sulfometuron-methyl” p. 92, “triasulfuron” p. 94, “ametryn” p. 198,“atrazine” p. 188, “aziprotryne” p. 206, “cyanazine” p. 192, “cyprazine”p. 192, “desmetryne” p. 200, “dipropetryn” p. 202, “eglinazine-ethyl” p.208, “hexazinon” p. 208, procyazine” p. 192, “prometone” p. 196,“prometryn” p. 196, “propazine” p. 188, “secbumeton” p. 196, “simazine”p. 188, “simetryn” p. 196, “terbumeton” p. 204, “terbutryn” p. 198,“terbuthylazine” p. 190, “trietazine” p. 188, “ethiozin” p. 210,“metamitron” p. 206, “metribuzin” p. 202, “bromacil” p. 180, “lenacil”p. 180, “terbacil” p. 180, “benazolin” p. 262, “bensulide” p. 228,“benzofluor” p. 266, “butamifos” p. 228, “DCPA” p. 28, “dichlobenil” p.148, “endothal” p. 264, “mefluididen” p. 306, “perfluidone” p. 260,“terbuchlor” p. 48 or in “Global Herbicide Directory” First Edition,1994 see “oxadiargyl” p. 96, or in “European Directory of AgrochemicalProducts Volume 2—Herbicides” Fourth Edition, see “buminafos” p. 255.The compound “DEH-112” is disclosed in European Patent Application EP 0302 203. The compound “caloxydim” is described in DE 3 336 140, thecompound “cinidon-ethyl” in DE 3 603 789 and the compound“fluorbentranil” in EP 84 893. Other-compounds are known from “BrightonCrop Protection Conference—Weeds—1993 (see “thidiazimin” p. 29,“AC-322140” p. 41, “KIH-6127” p. 47, “prosulfuron” p. 53, “KIH-2023” p.61, “metobenzuron” p. 67). The compound “CH-900” is described in EP 0332 133.

[0004] In principle, it is desirable in crop protection products toincrease the specific activity of an active ingredient and thereliability of its action. It was therefore the object of the presentinvention to increase the activity of known, herbicidallyactive-sulfonylureas of the formula I.

[0005] We have found that this object is achieved by a herbicidalmixture which comprises

[0006] a) at least one derivative of the sulfonylurea of the formula I

[0007]  where the substituents have the following meanings:

[0008] R¹ is C₁-C₆-alkyl which has attached to it one to five of thefollowing groups: methoxy, ethoxy, SO₂CH₃, cyano, chlorine, fluorine,SCH₃, S(O)CH₃;

[0009] halogen;

[0010] a group ER⁶ where E is O, S or NR⁷;

[0011] COOR⁸;

[0012] NO₂;

[0013] S(O)_(o)R⁹, SO₂NR¹⁰R¹¹, CONR¹⁰R¹¹;

[0014] R² is hydrogen, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl,halogen, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; C₁-C₄-haloalkyl, aC₁-C₂-alkylsulfonyl group, nitro, cyano or C₁-C₄-alkylthio;

[0015] R³ is F, CF₃, CF₂Cl, CF₂H, OCF₃, OCF₂Cl, or, if R¹ is CO₂CH₃ andR² is simultaneosly fluorine, R³ is Cl, or, if R¹ is CH₂CF₃ or CF₂CF₃,R³ is methyl, or, if R⁴ is OCF₃ or OCF₂Cl, R³ is OCF₂H or OCF₂Br;

[0016] R⁴ is C₁-C₂-alkoxy, C₁-C₂-alkyl, C₁-C₂-alkylthio,C₁-C₂-alkylamino, di-C₁-C₂-alkylamino, halogen, C₁-C₂-haloalkyl,C₁-C₂-haloalkoxy,

[0017] R⁵ is hydrogen, C₁-C₂-alkoxy, C₁-C₄-alkyl;

[0018] R⁶ is C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl orC₃-C₆-cycloalkyl, all of which can have attached to them 1 to 5 halogenatoms, with the exception of allyl, difluoromethoxy,chlorodifluoromethoxy and 2-chloroethoxy, if E is O or S. In the eventthat E is O or NR⁷, R⁶ is furthermore also methylsulfonyl,ethylsulfonyl, trifluoromethylsulfonyl, allylsulfonyl, propargylsulfonylor dimethylsulfamoyl;

[0019] R⁷ is hydrogen, methyl or ethyl

[0020] R⁸ is a C₁-C₆-alkyl group which can have attached to it up tothree of the following radicals: halogen, C₁-C₄-alkoxy, C₁-C₄-alkylthio,C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₂-alkoxy, C₃-C₇-cycloalkyl and/orphenyl; a C₅-C₇-cycloalkyl group which can have attached to it up tothree C₁-C₄-alkyl groups; C₃-C₆-alkenyl or C₃-C₆-alkynyl;

[0021] R⁹ is a C₁-C₆-alkyl group which can have attached to it one tothree of the following radicals; halogen, C₁-C₄-alkoxy, C₁-C₄-alkylthio,C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₂-alkoxy, C₃-C₇-cycloalkyl and/orphenyl; a C₅-C₇-cycloalkyl group which can have attached to it one tothree C₁-C₄-alkyl groups; a C₃-C₆-alkenyl group or a C₃-C₆-alkynylgroup;

[0022] R¹⁰ is hydrogen, a C₁-C₂-alkoxy group, a C₁-C₆-alkyl group, ortogether with R¹¹ is a C₄-C₆-alkylene chain in which one methylene groupcan be replaced by an oxygen atom or a C₁-C₄-alkylimino group;

[0023] R¹¹ is a C₁-C₄-alkyl group which can have attached to it one tofour halogen or C₁-C₄-alkoxy radicals; C₃-C₆-cycloalkyl

[0024] n is 0-3

[0025] o is 1-2

[0026] Z N or CH, and

[0027] b) a synergistically active amount of at least one herbicidalcompound selected from the groups b1 to b41

[0028] b1 1,3,4-thiadiazoles:

[0029] buthidazole, cyprazole

[0030] b2 amides:

[0031] allidochlor (CDAA), benzoylprop-ethyl, bromobutide, chlorthiamid,dimepiperate, dimethenamid, diphenamid, etobenzanid (benzchlomet),flamprop-methyl, fosamin, isoxaben, monalide, naptalame, pronamid(propyzamid), propanil

[0032] b3 aminophosphoric acids:

[0033] bilanafos, (bialaphos), buminafos, glufosinate-ammonium,glyphosate, sulfosate

[0034] b4 aminotriazoles:

[0035] amitrol

[0036] b5 anilides:

[0037] anilofos, mefenacet

[0038] b6 aryloxyalkanoic acids:

[0039] 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P,dichlorprop-P (2,4-DP-P), fenoprop (2,4,5-TP), fluoroxypyr, MCPA, MCPB,mecoprop, mecoprop-P, napropamide, napropanilide, triclopyr

[0040] b7 benzoic acids:

[0041] chloramben, dicamba

[0042] b8 benzothiadiazinones:

[0043] bentazone

[0044] b9 bleaches:

[0045] clomazone (dimethazone), diflufenican, fluorochloridone,flupoxam, fluridone, pyrazolate, sulcotrione (chlormesulone)

[0046] b10 carbamates:

[0047] asulam, barban, butylate, carbetamid, chlorbufam, chlorpropham,cycloate, desmedipham, di-allate, EPTC, esprocarb, molinate, orbencarb,pebulate, phenisopham, phenmedipham, propham, prosulfocarb,pyributicarb, sulf-allate (CDEC), terbucarb, thiobencarb (benthiocarb),tiocarbazil, tri-allate, vernolate

[0048] b11 quinolinecarboxylic acids:

[0049] quinclorac, quinmerac

[0050] b12 chloracetanilides:

[0051] acetochlor, alachlor, butachlor, butenachlor, diethatylethyl,dimethachlor, metazachlor, metolachlor, pretilachlor, propachlor,prynachlor, terbuchlor, thenylchlor, xylachlor

[0052] b13 cyclohexenones:

[0053] alloxydim, caloxydim, clethodim, cloproxydim, cycloxydim,sethoxydim, tralkoxydim,2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one

[0054] b14 dichloropropionic acids:

[0055] dalapon

[0056] b15 dihydrobenzofurans:

[0057] ethofumesate

[0058] b16 dihydrofuran-3-ones:

[0059] flurtamone

[0060] b17 dinitroanilines:

[0061] benefin, butralin, dinitramin, ethalfluralin, fluchloralin,isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin,trifluralin

[0062] b18 dinitrophenols:

[0063] bromofenoxim, dinoseb, dinoseb-acetate, dinoterb, DNOC

[0064] b19 diphenyl ethers:

[0065] acifluorfen-sodium, aclonifen, bifenox, chlornitrofen (CNP),difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen,furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen

[0066] b20 dipyridylenes:

[0067] cyperquat, difenzoquat methylsulfate, diquat, paraquat dichloride

[0068] b21 ureas:

[0069] benzthiazuron, buturon, chlorbromuron, chloroxuron, chlortoluron,cumyluron, dibenzyluron, cycluron, dimefuron, diuron, dymrone,ethidimuron, fenuron, fluometuron, isoproturon, isouron, karbutilate,linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron,monuron, neburon, siduron, tebuthiuron, trimeturon

[0070] b22 imidazoles:

[0071] isocarbamid

[0072] b23 imidazolinones:

[0073] imazamethapyr, imazapyr, imazaquin, imazethabenz-methyl(imazame), imazethapyr

[0074] b24 oxadiazoles:

[0075] methazole, oxadiargyl, oxadiazon

[0076] b25 oxiranes:

[0077] tridiphane

[0078] b26 phenols:

[0079] bromoxynil, ioxynil

[0080] b27 phenoxyphenoxypropionic esters:

[0081] clodinafop, cyhalofop-butyl, diclofop-methyl, fenoxapropethyl,fenoxaprop-P-ethyl, fenthiapropethyl, fluazifopbutyl, fluazifop-P-butyl,haloxyfop-ethoxyethyl, haloxyfop-methyl, halofopop-P-methyl,isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-P-ethyl,quizalofoptefuryl

[0082] b28 phenylacetic acids:

[0083] chlorfenac (fenac)

[0084] b29 phenylpropionic acid:

[0085] chlorophenprop-methyl

[0086] b30 protoporphyrinogen IX oxydase inhibitors:

[0087] benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin,flumipropyn, flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone,thidiazimin

[0088] b31 pyrazoles:

[0089] nipyraclofen

[0090] b32 pyridazines:

[0091] chloridazon, maleic hydrazide, norflurazon, pyridate

[0092] b33 pyridinecarboxylic acids:

[0093] clopyralid, dithiopyr, picloram, thiazopyr

[0094] b34 pyrimidyl ethers:

[0095] pyrithiobac acid, pyrithiobac sodium, KIH-2023, KIH-6127

[0096] b35 sulfonamides:

[0097] flumetsulam, metosulam

[0098] b36 sulfonylureas:

[0099] amidosulfuron, azimsulfuron, bensulfuron-methyl,chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron,ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron,halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron,primisulfuron, prosulfuron, pyrazo-sulfuron-ethyl, rimsulfuron,sulfometuron-methyl, thifensulfuron-methyl, triasulfuron,tribenuron-methyl, triflusulfuron-methyl

[0100] b37 triazines:

[0101] ametryn, atrazine, aziprotryn, cyanazine, cyprazine, desmetryn,dimethamethryn, dipropetryn, eglinazine-ethyl, hexazinon, procyazine,prometon, prometryn, propazine, secbumeton, simazine, simetryn,terbumeton, terbutryn, terbuthylazine, trietazine

[0102] b38 triazinones:

[0103] ethiozin, metamitron, metribuzin

[0104] b39 triazolecarboxamides:

[0105] triazofenamid

[0106] b40 uracils:

[0107] bromacil, lenacil, terbacil

[0108] b41 others:

[0109] benazolin, benfuresate, bensulide, benzofluor, butamifos,cafenstrole, chlorthal-dimethyl (DCPA), cinmethylin, dichlobenil,endothall, fluorbentranil, mefluidide, perfluidone, piperophos

[0110] or their environmentally compatible salts.

[0111] The herbicidal mixture according to the invention hassuperadditive synergistic action and is selective for those crop plantswhich also tolerate the individual compounds themselves.

[0112] Especially preferred sulfonylureas of the formula I with a viewto their synergistic herbicidal action are those where

[0113] R¹ is CO₂CH₃, CO₂C₂H₅, CO₂iC₃H₇, CF₃, CF₂H; OSO₂CH₃, OSO₂N(CH₃)₂,Cl, NO₂, SO₂N(CH₃)₂, SO₂CH₃ and N(CH₃)SO₂CH₃

[0114] R² is hydrogen, Cl, F or C₁-C₂-alkyl

[0115] R³ is CF₂H, OCF₃, OCF₂Cl, CF₂Cl, CF₃ or F

[0116] R⁴ is OCH₃, OC₂H₅, OCF₃, OCF₂Cl; CF₃, Cl, F, NH(CH₃), N(CH₃)₂ orC₁-C₂-alkyl

[0117] R⁵ is hydrogen,

[0118] Z is N or CH and

[0119] 0 or 1.

[0120] Preferred compounds of the formula I are compiled in the tablewhich follows. TABLE

No. R¹ R² R⁵ R³ R⁴ Z 1 CO₂CH₃ H H OCF₂Cl OCH₃ CH 2 CO₂C₂H₅ H H OCF₂ClOCH₃ CH 3 CO₂iC₃H₇ H H OCF₂Cl OCH₃ CH 4 NO₂ H H OCF₂Cl OCH₃ CH 5 SO₂CH₃H H OCF₂Cl OCH₃ CH 6 SO₂N(CH₃)₂ H H OCF₂Cl OCH₃ CH 7 Cl H H OCF₂Cl OCH₃CH 8 N(CH₃)SO₂CH₃ H H OCF₂Cl OCH₃ CH 9 OSO₂CH₃ H H OCF₂Cl OCH₃ CH 10OSO₂N(CH₃)₂ H H OCF₂Cl OCH₃ CH 11 CF₃ H H OCF₂Cl OCH₃ CH 12 CF₂H H HOCF₂Cl OCH₃ CH 13 CO₂CH₃ H H OCF₃ OCH₃ CH 14 CO₂C₂H₅ H H OCF₃ OCH₃ CH 15CO₂iC₃H₇ H H OCF₃ OCH₃ CH 16 NO₂ H H OCF₃ OCH₃ CH 17 SO₂CH₃ H H OCF₃OCH₃ CH 18 SO₂N(CH₃)₂ H H OCF₃ OCH₃ CH 19 Cl H H OCF₃ OCH₃ CH 20N(CH₃)SO₂CH₃ H H OCF₃ OCH₃ CH 21 OSO₂CH₃ H H OCF₃ OCH₃ CH 22 OSO₂N(CH₃)₂H H OCF₃ OCH₃ CH 23 CF₃ H H OCF₃ OCH₃ CH 24 CF₂H H H OCF₃ OCH₃ CH 25CO₂CH₃ H H F OCH₃ CH 26 CO₂C₂H₅ H H F OCH₃ CH 27 CO₂iC₃H₇ H H F OCH₃ CH28 NO₂ H H F OCH₃ CH 29 SO₂CH₃ H H F OCH₃ CH 30 SO₂N(CH₃)₂ H H F OCH₃ CH31 Cl H H F OCH₃ CH 32 N(CH₃)SO₂CH₃ H H F OCH₃ CH 33 OSO₂CH₃ H H F OCH₃CH 34 OSO₂N(CH₃)₂ H H F OCH₃ CH 35 CF₃ H H F OCH₃ CH 36 CF₂H H H F OCH₃CH 37 CO₂CH₃ H H CF₃ OCH₃ N 38 CO₂C₂H₅ H H CF₃ OCH₃ N 39 CO₂iC₃H₇ H HCF₃ OCH₃ N 40 NO₂ H H CF₃ OCH₃ N 41 SO₂CH₃ H H CF₃ OCH₃ N 42 SO₂N(CH₃)₂H H CF₃ OCH₃ N 43 Cl H H CF₃ OCH₃ N 44 N(CH₃)SO₂CH₃ H H CF₃ OCH₃ N 45OSO₂CH₃ H H CF₃ OCH₃ N 46 OSO₂N(CH₃)₂ H H CF₃ OCH₃ N 47 CF₃ H H CF₃ OCH₃N 48 CF₂H H H CF₃ OCH₃ N 49 CO₂CH₃ H H CF₃ OCH₃ CH 50 CO₂C₂H₅ H H CF₃OCH₃ CH 51 CO₂iC₃H₇ H H CF₃ OCH₃ CH 52 NO₂ H H CF₃ OCH₃ CH 53 SO₂CH₃ H HCF₃ OCH₃ CH 54 SO₂N(CH₃)₂ H H CF₃ OCH₃ CH 55 Cl H H CF₃ OCH₃ CH 56N(CH₃)SO₂CH₃ H H CF₃ OCH₃ CH 57 OSO₂CH₃ H H CF₃ OCH₃ CH 58 OSO₂N(CH₃)₂ HH CF₃ OCH₃ CH 59 CF₃ H H CF₃ OCH₃ CH 60 CF₂H H H CF₃ OCH₃ CH 61 CO₂CH₃ HH CF₂H OCH₃ N 62 CO₂C₂H₅ H H CF₂H OCH₃ N 63 CO₂iC₃H₇ H H CF₂H OCH₃ N 64NO₂ H H CF₂H OCH₃ N 65 SO₂CH₃ H H CF₂H OCH₃ N 66 SO₂N(CH₃)₂ H H CF₂HOCH₃ N 67 Cl H H CF₂H OCH₃ N 68 N(CH₃)SO₂CH₃ H H CF₂H OCH₃ N 69 OSO₂CH₃H H CF₂H OCH₃ N 70 OSO₂N(CH₃)₂ H H CF₂H OCH₃ N 71 CF₃ H H CF₂H OCH₃ N 72CF₂H H H CF₂H OCH₃ N 73 CO₂CH₃ H H CF₂H OCH₃ CH 74 CO₂C₂H5 H H CF₂H OCH₃CH 75 CO₂iC₃H₇ H H CF₂H OCH₃ CH 76 NO₂ H H CF₂H OCH₃ CH 77 SO₂CH₃ H HCF₂H OCH₃ CH 78 SO₂N(CH₃)₂ H H CF₂H OCH₃ CH 79 Cl H H CF₂H OCH₃ CH 80N(CH₃)SO₂CH₃ H H CF₂H OCH₃ CH 81 OSO₂CH₃ H H CF₂H OCH₃ CH 82 OSO₂N(CH₃)₂H H CF₂H OCH₃ CH 83 CF₃ H H CF₂H OCH₃ CH 84 CF₂H H H CF₂H OCH₃ CH 85CO₂CH₃ H H CF₂Cl OCH₃ N 86 CO₂C2H₅ H H CF₂Cl OCH₃ N 87 CO₂iC₃H₇ H HCF₂Cl OCH₃ N 88 NO₂ H H CF₂Cl OCH₃ N 89 SO₂CH₃ H H CF₂Cl OCH₃ N 90SO₂N(CH₃)₂ H H CF₂Cl OCH₃ N 91 Cl H H CF₂Cl OCH₃ N 92 N(CH₃)SO₂CH₃ H HCF₂Cl OCH₃ N 93 OSO₂CH₃ H H CF₂Cl OCH₃ N 94 OSO₂N(CH₃)₂ H H CF₂Cl OCH₃ N95 CF₃ H H CF₂Cl OCH₃ N 96 CF₂H H H CF₂Cl OCH₃ N 97 CO₂CH₃ 3-F H Cl OCH₃CH 98 CF₂CF₃ H H CH₃ OCH₃ N 99 CF₂CF₃ H H CH₃ OCH₃ N 100 SO₂C₂H₅ H H FOCH₃ CH

[0121] Examples of preferred compounds (b) are

[0122] bromobutide

[0123] dimethenamid

[0124] isoxaben

[0125] propanil

[0126] glufosinate-ammonium

[0127] glyphosate

[0128] sulfosate

[0129] mefenacet

[0130] 2,4-D

[0131] 2,4-DB

[0132] 2,4-DBEE

[0133] dichlorprop

[0134] dichlorprop-P

[0135] dichlorprop-P (2,4-DP-P)

[0136] fluroxypyr

[0137] MCPA

[0138] mecoprop

[0139] mecoprop-P

[0140] dicamba

[0141] bentazone

[0142] clomazone

[0143] diflufenican

[0144] sulcotrione

[0145] phenmedipham

[0146] thiobencarb

[0147] quinclorac

[0148] quinmerac

[0149] acetochlor

[0150] alachlor

[0151] butachlor

[0152] metazachlor

[0153] metolachlor

[0154] pretilachlor

[0155] butroxydim

[0156] caloxydim

[0157] clethodim

[0158] cycloxydim

[0159] sethoxydim

[0160] tralkoxydim

[0161]2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one

[0162] pendimethalin

[0163] acifluorfen-sodium

[0164] bifenox

[0165] fluoroglycofen-ethyl

[0166] fomesafen

[0167] lactofen

[0168] chlortoluron

[0169] cycluron

[0170] dymrone

[0171] isoproturon

[0172] methabenzthiazuron

[0173] imazaquin

[0174] imazethabenz-methyl

[0175] imazethapyr

[0176] bromoxynil

[0177] ioxynil

[0178] clodinafop

[0179] cyhalofop-butyl

[0180] fenoxyprop-ethyl

[0181] fenoxaprop-P-ethyl

[0182] haloxyfop-P-methyl

[0183] cinidon-ethyl

[0184] flumiclorac-pentyl

[0185] flumipropyn

[0186] fluthiacet-methyl

[0187] pyridate

[0188] clopyralid

[0189] bispyribac-sodium

[0190] KIH-8555

[0191] KUH-920

[0192] flumetsulam

[0193] metosulam

[0194] amidosulfuron

[0195] azimsulfuron

[0196] bensulfuron-methyl

[0197] chlorimuron-ethyl

[0198] chlorsulfuron

[0199] cinosulfuron

[0200] cyclosulfamuron

[0201] ethoxysulfuron

[0202] flazasulfuron

[0203] halosulfuron-methyl

[0204] HOE-107925

[0205] imazosulfuron

[0206] metsulfuron-methyl

[0207] nicosulfuron

[0208] primisulfuron

[0209] prosulfuron

[0210] pyrazosulfuron-ethyl

[0211] rimsulfuron

[0212] thifensulfuron-methyl

[0213] triasulfuron

[0214] tribenuron-methyl

[0215] atrazine

[0216] cyanazine

[0217] terbuthylazine

[0218] benazolin

[0219] benfuresate

[0220] cafenstrole

[0221] cinemthylin

[0222] ammonium-bentazone

[0223] cloquintocet

[0224] ET-751

[0225] F-8426

[0226] KPP-314

[0227] The following compounds are particularly preferred:

[0228] 2,4-D

[0229] dichlorprop-P

[0230] MCPA

[0231] mecoprop-P

[0232] dicamba

[0233] bentazone

[0234] diflufenican

[0235] sulcotrione

[0236] quinclorac

[0237] caloxydim

[0238] cycloxydim

[0239] sethoxydim

[0240]2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one

[0241] acifluorfen-sodium

[0242] fluoroglycofen-ethyl

[0243] bromoxynil

[0244] fenoxyprop-ethyl

[0245] cinidon-ethyl

[0246] amidosulfuron

[0247] bensulfuron-methyl

[0248] metsulfuron-methyl

[0249] nicosulfuron

[0250] pyrazosulfuron-ethyl

[0251] rimsulfuron

[0252] triasulfuron

[0253] tribenuron-methyl

[0254] atrazine

[0255] terbuthylazine

[0256] ammonium-bentazone

[0257] cloquintocet

[0258] The following compounds are very especially preferred:

[0259] dichlorprop-P

[0260] mecoprop-P

[0261] ammonium-bentazone

[0262] bentazone

[0263] diflufenican

[0264] quinclorac

[0265]2-(1-[2-(4-chlorophenoxy)propyloxyimino]butyl)-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one

[0266] caloxydim

[0267] cycloxydim

[0268] sethoxydim

[0269] fluoroglycofen-ethyl

[0270] cinidon-ethyl

[0271] nicosulfuron

[0272] pyrazosulfuron-ethyl

[0273] rimsulfuron

[0274] atrazine

[0275] terbuthylazine.

[0276] The present invention also relates to herbicidal compositionswhich comprise at least one herbicidally active amount of a sulfonylurea(a) of the above-described formula I or their environmentally compatiblesalts, a synergistically active amount of at least one above-describedherbicidal compound (b) or its environmentally compatible salts, atleast one liquid and/or solid carrier and, if desired, at least oneadjuvant.

[0277] In the herbicidal mixtures and herbicidal compositions accordingto the invention, the sulfonylureas of the formula I or theirenvironmentally compatible salts and the herbicidal compounds (b) ortheir environmentally compatible salts are used in such weight ratiosthat the desired synergistic effect is observed. The mixing ratios ofsulfonylurea of the formula I and a herbicidal compound (b) arepreferably 1 to 1:0.1 to 1:40, in particular 1:0.2 to 1:20, especiallypreferably 1:0.5 to 1:15.

[0278] The herbicidal mixtures and herbicidal compositions according tothe invention which comprise the sulfonylureas of the formula I or theirenvironmentally compatible salts of, for example, alkali metals,alkaline earth metals or ammonia and amines and the herbicidal compounds(b) or their environmentally compatible salts of, for example, alkalimetals, alkaline earth metals or ammonia and amines are capable ofeffecting very good control of broadleaved weeds and grass weeds in thecrop rice without damaging the crop plants, an effect which is observedeven when low rates of application are used.

[0279] Taking into consideration the versatility of the applicationmethods, the herbicidal mixtures and herbicidal compositions accordingto the invention can also be employed in a further number of crop plantsfor eliminating undesirable plants. Suitable crops are, for example, thefollowing:

[0280]Allium cepa, Ananas comosus, Arachis hypogaea, Asparagusofficinalis, Beta vulgaris ssp. altissima, Beta vulgaris ssp. rapa,Brassica napus var. napus, Brassica napus var. napobrassica, Brassicarapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Caryaillinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffeacanephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucuscarota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypiumhirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypiumvitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare,Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linumusitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta,Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Oleaeuropaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Piceaabies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyruscommunis, Ribes sylvestre, Ricinus communis, Saccharum officinarum,Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare),Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum,Vicia faba, Vitis vinifera, Zea mays,

[0281] In addition, the herbicidal mixtures and herbicidal compositionsaccording to the invention can also be used in crops which tolerate theaction of herbicides due to breeding, including genetic engineeringmethods.

[0282] The herbicidal mixtures and herbicidal compositions according tothe invention may be applied pre- or post-emergence. If the activeingredients are less well tolerated by certain crop plants, applicationtechniques may be used in which the herbicidal compositions are sprayed,with the aid of the spraying equipment, in such a way that the activeingredients reach the leaves of the sensitive crop plants as little aspossible while reaching the leaves of undesirable plants which growunderneath, or the bare soil surface (post-directed, lay-by).

[0283] The compositions according to the invention can be applied, forexample in the form of ready-to-spray aqueous solutions, powders,suspensions, also highly-concentrated aqueous, oily or other suspensionsor dispersions, emulsions, oil dispersions, pastes, dusts, materials forspreading or granules, by means of spraying, atomizing, dusting,spreading or pouring. The use forms depend on the intended purposes; inany case, they should guarantee the finest possible distribution of theactive ingredients according to the invention.

[0284] Suitable inert additives are mineral oil fractions of medium tohigh boiling point, such as kerosene or diesel oil, furthermore coal taroils and oils of vegetable or animal origin, aliphatic, cyclic andaromatic hydrocarbons, eg. paraffin, tetrahydronaphthalene, alkylatednaphthalenes or their derivatives, alkylated benzenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone or strongly polar solvents such as N-methylpyrrolidone orwater.

[0285] Aqueous use forms can be prepared from emulsion concentrates,suspensions, pastes, wettable powders or water-dispersible granules byadding water. To prepare emulsions, pastes or oil dispersions, thesubstances, as such or dissolved in an oil or solvent, can behomogenized in water by means of wetting agent, adhesive, dispersant oremulsifier. Alternatively, it is possible to prepare concentratescomposed of active ingredient, wetting agent, adhesive, dispersant oremulsifier and, if desired, solvent or oil, which are suitable fordilution with water.

[0286] Suitable surfactants are the alkali, alkaline earth and ammoniumsalts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- anddibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- andalkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, andsalts of sulfated hexa-, hepta- and octadecanols, and of fatty alcoholglycol ethers, condensates of sulfonated naphthalene and its derivativeswith formaldehyde, condensates of naphthalene or of thenaphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyleneoctylphenol ether, ethoxylated isooctylphenol, octylphenol ornonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycolether, alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, laurylalcohol polyglycol ether acetate, sorbitol esters, lignosulfite wasteliquors or methylcellulose.

[0287] Powders, materials for spreading, and dusts, can be prepared bymixing or concomitantly grinding the herbicidal mixture with a solidcarrier.

[0288] Granules, eg. coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active ingredientonto solid carriers. Solid carriers are mineral earths such as silicas,silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground synthetic materials, fertilizers suchas ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, andproducts of vegetable origin such as cereal meal, tree bark meal, woodmeal and nutshell meal, cellulose powders, or other solid carriers.

[0289] In general, the formulations comprise 0.01 to 95% by weight,preferably 0.5 to 90% by weight, of the herbicidal mixture.

[0290] It may furthermore be advantageous to apply the herbicidalmixtures and herbicidal compositions according to the invention togetherin the form of a mixture with other crop protection agents, for examplewith agents for controlling pests or phytopathogenic fungi or bacteria.Also of interest is the miscibility with mineral salt solutions, whichare employed for treating nutritional and trace element deficiencies.Non-phytotoxic oils and oil concentrates may also be added.

[0291] The rates of application of pure herbicidal mixture, ie. withoutformulation auxiliaries, are from 0.01 to 5 kg/ha, preferably 0.03 to 4kg/ha, especially preferably 0.1 to 3.0 kg/ha, of active ingredient(a.i.), depending on the intended purpose, the season, the target plantsand the growth stage.

[0292] The herbicidal compositions according to the invention areapplied to the plants mainly by means of foliar sprays. They may beapplied by customary spraying techniques using amounts of approximately100 to 1000 l of spray mixture per ha, for example using water as thecarrier. An application of the compositions in the so-called“low-volume” and “ultra-low-volume” method is also possible, as is theirapplication in the form of so-called granules.

USE EXAMPLES

[0293] The herbicide mixtures were applied post-emergence (foliartreatment), the sulfonylurea derivatives being applied in the form of 10to 75 percent granules and the herbicidal compounds (b) in theformulation in which they exist as the commercial product.

[0294] The tests involved field trials with small plots at a sandy loamsite (pH 6.2 to 7.0) or sandy clay (pH 5.0 to 6.7) site.

[0295] The weeds were present in different sizes and development stages,their height being, on average, 5 to 20 cm, depending on the planthabit.

[0296] The herbicidal compositions were applied alone and also jointly,in the latter case sometimes as a tank mix, sometimes as a ready-mix.This was done using water (350 l/ha) as the distribution vehicle,depending on the formulation of the active ingredients in the form ofemulsions, aqueous solutions or suspensions. Application was effectedwith the aid of a mobile plot sprayer.

[0297] The test period extended over 3 to 8 weeks, and the stands werealso observed at later dates.

[0298] The damage caused by the herbicidal compositions was assessedusing a scale from 0% to 100% in comparison with untreated controlplots. Thus, 0 means no damage, and 100 means complete destruction ofthe plants.

[0299] The examples which follow show the activity of the herbicidalcompositions which can be used according to the invention withoutexcluding the possibility of other uses.

[0300] In these examples, the method of S. R. Colby (1967): Calculatingsynergistic and antagonistic responses of herbicide combinations, Weeds15, 20 et seq. was used to determine the value E which can be expectedwhen an action of the individual active ingredients is merely additive.

[0301] The calculation was carried out using the formula$E = {X + Y - \frac{XY}{100}}$

[0302] where

[0303] X=percentage activity using preparation A at a rate ofapplication a

[0304] Y=percentage activity using preparation B at a rate ofapplication b

[0305] E=expected activity (in %) caused by A+B at rate of applicationof a+b.

[0306] If the observed value exceeds the value E calculated usingColby's formula, a synergistic effect is present.

[0307] The herbicidal compositions according to the invention have aherbicidal activity which is higher than what can be expected whenapplying Colby's formula compared with the observed activities of theindividual components . . . used alone.

We claim:
 1. A herbicidal mixture comprising a) at least one derivativeof a sulfonylurea of the formula I

 where the substituents have the following meanings: R¹ is C₁-C₆-alkylwhich has attached to it one to five of the following groups: methoxy,ethoxy, SO₂CH₃, cyano, chlorine, fluorine, SCH₃, S(O)CH₃; halogen; agroup ER⁶ where E is O, S or NR⁷; COOR⁸; NO₂; S(O)_(o)R⁹, SO₂NR¹⁰R¹¹,CONR¹⁰R¹¹; R² is hydrogen, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl,halogen, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; C₁-C₄-haloalkyl, aC₁-C₂-alkylsulfonyl group, nitro, cyano or C₁-C₄-alkylthio; R³ is F,CF₃, CF₂Cl, CF₂H, OCF₃, OCF₂Cl, or, if R¹ is CO₂CH₃ and R² issimultaneosly fluorine, R³ is Cl, or, if R¹ is CH₂CF₃ or CF₂CF₃, R³ ismethyl, or, if R⁴ is OCF₃ or OCF₂Cl, R³ is OCF₂H or OCF₂Br; R⁴ isC₁-C₂-alkoxy, C₁-C₂-alkyl, C₁-C₂-alkylthio, C₁-C₂-alkylamino,di-C₁-C₂-alkylamino, halogen, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, R⁵ ishydrogen, C₁-C₂-alkoxy, C₁-C₄-alkyl; R⁶ is C₁-C₄-alkyl, C₂-C₄-alkenyl,C₂-C₄-alkynyl or C₃-C₆-cycloalkyl, all of which can have attached tothem 1 to 5 halogen atoms, with the exception of allyl, difluoromethoxy,chlorodifluoromethoxy and 2-chloroethoxy, if E is O or S. In the eventthat E is O or NR⁷, R⁶ is furthermore also methylsulfonyl,ethylsulfonyl, trifluoromethylsulfonyl, allylsulfonyl, propargylsulfonylor dimethylsulfamoyl; R⁷ is hydrogen, methyl or ethyl R⁸ is aC₁-C₆-alkyl group which can have attached to it up to three of thefollowing radicals: halogen, C₁-C₄-alkoxy, C₁-C₄-alkylthio,C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₂-alkoxy, C₃-C₇-cycloalkyl and/orphenyl; a C₅-C₇-cycloalkyl group which can have attached to it up tothree C₁-C₄-alkyl groups; C₃-C₆-alkenyl or C₃-C₆-alkynyl; R⁹ is aC₁-C₆-alkyl group which can have attached to it one to three of thefollowing radicals: halogen, C₁-C₄-alkoxy, C₁-C₄-alkylthio,C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₂-alkoxy, C₃-C₇-cycloalkyl and/orphenyl; a C₅-C₇-cycloalkyl group which can have attached to it one tothree C₁-C4-alkyl groups; C₃-C₆-alkenyl or C₃-C₆-alkynyl; R¹⁰ ishydrogen, C₁-C₂-alkoxy, C₁-C₆-alkyl, or together with R¹¹ is aC₄-C₆-alkylene chain in which one methylene group can be replaced by anoxygen atom or a C₁-C₄-alkylimino group; R¹¹ is a C₁-C₄-alkyl groupwhich can have attached to it one to four halogen or C₁-C₄-alkoxyradicals; C₃-C6-cycloalkyl n is 0-3 o is 1-2 Z N or CH, or theirenvironmentally compatible salts and b) a synergistically active amountof at least one herbicidal compound selected from groups b1 to b41 b11,3,4-thiadiazoles: buthidazole, cyprazole b2 amides: allidochlor(CDAA), benzoylprop-ethyl, bromobutide, chlorthiamid, dimepiperate,dimethenamid, diphenamid, etobenzanid (benzchlomet), flamprop-methyl,fosamin, isoxaben, monalide, naptalame, pronamid (propyzamid), propanilb3 aminophosphoric acids: bilanafos, (bialaphos), buminafos,glufosinate-ammonium, glyphosate, sulfosate b4 aminotriazoles: amitrolb5 anilides: anilofos, mefenacet b6 aryloxyalkanoic acids: 2,4-D,2,4-DB, clomeprop, dichlorprop, dichlorprop-P, dichlorprop-P (2,4-DP-P),fenoprop (2,4,5-TP), fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P,napropamide, napropanilide, triclopyr b7 benzoic acids: chloramben,dicamba b8 benzothiadiazinones: bentazone b9 bleaches: clomazone(dimethazone), diflufenican, fluorochloridone, flupoxam, fluridone,pyrazolate, sulcotrione (chlormesulone) b10 carbamates: asulam, barban,butylate, carbetamid, chlorbufam, chlorpropham, cycloate, desmedipham,di-allate, EPTC, esprocarb, molinate, orbencarb, pebulate, phenisopham,phenmedipham, propham, prosulfocarb, pyributicarb, sulf-allate (CDEC),terbucarb, thiobencarb (benthiocarb), tiocarbazil, tri-allate, vernolateb11 quinolinecarboxylic acids: quinclorac, quinmerac b12chloracetanilides: acetochlor, alachlor, butachlor, butenachlor,diethatyl-ethyl, dimethachlor, metazachlor, metolachlor, pretilachlor,propachlor, prynachlor, terbuchlor, thenylchlor, xylachlor b13cyclohexenones: alloxydim, caloxydim, clethodim, cloproxydim,cycloxydim, sethoxydim, tralkoxydim,2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-oneb14 dichlorpropionic acids: dalapon b15 dihydrobenzofurans: ethofumesateb16 dihydrofuran-3-ones: flurtamone b17 dinitroanilines: benefin,butralin, dinitramin, ethalfluralin, fluchloralin, isopropalin,nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralinb18 dinitrophenols: bromofenoxim, dinoseb, dinoseb-acetat, dinoterb,DNOC b19 diphenyl ethers: acifluorfen-sodium, aclonifen, bifenox,chlornitrofen (CNP), difenoxuron, ethoxyfen, fluorodifen,fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen,nitrofluorfen, oxyfluorfen b20 dipyridylenes: cyperquat, difenzoquatmethylsulfate, diquat, paraquat dichloride b21 ureas: benzthiazuron,buturon, chlorbromuron, chloroxuron, chlortoluron, cumyluron,dibenzyluron, cycluron, dimefuron, diuron, dymrone, ethidimuron,fenuron, fluometuron, isoproturon, isouron, karbutilate, linuron,methabenzthiazuron, metobenzuron, metoxuron, monolinuron, monuron,neburon, siduron, tebuthiuron, trimeturon b22 imidazoles: isocarbamidb23 imidazolinones: imazamethapyr, imazapyr, imazaquin,imazethabenz-methyl (imazame), imazethapyr b24 oxadiazoles: methazole,oxadiargyl, oxadiazon b25 oxiranes: tridiphane b26 phenols: bromoxynil,ioxynil b27 phenoxyphenoxypropionic esters: clodinafop, cyhalofop-butyl,diclofopmethyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenthiapropethyl,fluazifop-butyl, fluazifop-P-butyl, haloxyfopethoxyethyl,haloxyfop-methyl, haloxyfop-P-methyl, isoxapyrifop, propaquizafop,quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-tefuryl b28phenylacetic acids: chlorfenac (fenac) b29 phenylpropionic acid:chlorophenprop-methyl b30 protoporphyrinogen IX oxydase inhibitors:benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn,flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone, thidiaziminb31 pyrazoles: nipyraclofen b32 pyridazines: chloridazon, maleichydrazide, norflurazon, pyridate b33 pyridinecarboxylic acids:clopyralid, dithiopyr, picloram, thiazopyr b34 pyrimidyl ethers:pyrithiobac acid, pyrithiobac sodium, KIH-2023, KIH-6127 b35sulfonamides: flumetsulam, metosulam b36 sulfonylureas: amidosulfuron,azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron,cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron,flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl,nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl,rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron,tribenuron-methyl, triflusulfuron-methyl b37 triazines: ametryn,atrazine, aziprotryn, cyanazine, cyprazine, desmetryn, dimethamethryn,dipropetryn, eglinazine-ethyl, hexazinon, procyazine, prometon,prometryn, propazine, secbumeton, simazine, simetryn, terbumeton,terbutryn, terbuthylazine, trietazine b38 triazinones: ethiozin,metamitron, metribuzin b39 triazolecarboxamides: triazofenamid b40uracils: bromacil, lenacil, terbacil b41 others: benazolin, benfuresate,bensulide, benzofluor, butamifos, cafenstrole, chlorthal-dimethyl(DCPA), cinmethylin, dichlobenil, endothall, fluorbentranil, mefluidide,perfluidone, piperophos or their environmentally compatible salts.
 2. Aherbicidal mixture as claimed in claim 1, comprising a sulfonylurea ofthe formula I where R¹ is CO₂CH₃, CO₂C₂H₅, CO₂iC₃H₇, CF₃, CF₂H, CH₂CF₃,CF₂CF₃, OSO₂CH₃, OSO₂N(CH₃)₂, Cl, NO₂, SO₂N(CH₃)₂, SO₂CH₃, SO₂C₂H₅, andN(CH₃)SO₂CH₃, R² is hydrogen, halogen or methyl, R³ is CF₂H, OCF₃,OCF₂Cl, CF₃, or, if R¹ is CO₂CH₃ and R² is simultaneously fluorine, R³is Cl, or, if R¹ is F₃, CH₂CF₃ or CF₂CF₃, R³ is methyl, R⁴ is OCH₃, R⁵is hydrogen and Z is N or CH.
 3. A herbicidal mixture as claimed inclaim 1 or 2, comprising a sulfonylurea of the formula I where R¹ ishalogen, a group ER⁶, a group CO₂R⁸, SO₂CH₃ or SO₂C₂H₅, R² is hydrogen,R³ is F, R⁴ is OCF₃, OCF₂Cl, OCH₃, R⁵ is hydrogen, R⁶ and R⁸ have themeanings given in claim 1 and Z is N or CH.
 4. A herbicidal mixture asclaimed in any of claims 1 to 3, comprising a sulfonylurea of theformula I where R¹ is CF₃, R² is hydrogen, R³ is CF₃, R⁴ is OCH₃, R⁵ ishydrogen and Z is N.
 5. A herbicidal mixture as claimed in any of claims1 to 4, comprising at least one herbicidal compound (b) from the groupconsisting of bromobutide, dimethenamid, isoxaben, propanil,glufosinate-ammonium, glyphosate, sulfosate, mefenacet, 2,4-D,2,4-DB,2,4-DBEE, dichlorprop, dichlorprop-p (2,4-DP-P), fluroxypyr, MCPA,mecoprop, mecoprop-p, dicamba, bentazone, clomazone, diflufenican,sulcotrione, phenmedipham, thiobencarb, quinclorac, quinmerac,acetochlor, alachlor, butachlor, metazachlor, metolachlor, pretilachlor,butroxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, caloxydim,2-{1-[2-(4-chlorophenoxy)propyloxyi-mino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one,pendimethalin, acifluorfen-sodium, bifenox, fluoroglycofen-ethyl,fomesafen, lactofen, chlortoluron, cycluron, dymrone, isoproturon,methabenzthiazuron, imazaquin, imazethabenzmethyl, imazethapyr,bromoxynil, ioxynil, clodinafop, cyhalofop-butyl, fenoxyprop-ethyl,fenoxaprop-p-ethyl, haloxyfop-p-methyl, cinidon-ethyl,flumiclorac-pentyl, flumipropyn, fluthiacet-methyl, pyridate,clopyralid, bispyribac-sodium, KIH-8555, KUH-920, flumetsulam,metosulam, amidosulfuron, azimsulfuron, bensulfuron-methyl,chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron,ethoxysulfuron, flazasulfuron, galosulfuron-methyl, HOE-107925,imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron,prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, thifensulfuron-methyl,triasulfuron, tribenuron-methyl, atrazine, cyanazine, terbutylazin,benazolin, benfuresate, cafenstrole, cinmethylin, ammonium-bentazone,cloquintocet, ET-751, F-8426, KPP-314.
 6. A herbicidal mixture asclaimed in any of claims 1 to 5, comprising at least one herbicidalcompound (b) from the group consisting of 2,4-D, MCPA, dichlorprop-p,mecoprop-p, dicamba, bentazone, diflufenican, sulcotrione, quinclorac,caloxydim, cycloxydim, sethoxydim,2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one,acifluorfen-sodium, fluoroglycofen-ethyl, bromoxynil, fenoxyprop-ethyl,cinidon-ethyl, amidosulfuron, bensulfuron-methyl, metsulfuron-methyl,nicosulfuron, pyrazosulfuron-ethyl, rimsulfuron, triasulfuron,tribenuron-methyl, atrazine, terbuthylazine, ammonium-bentazone,cloquintocet.
 7. A herbicidal mixture as claimed in any of claims 1 to6, comprising a sulfonylurea (a) of the formula I and one or moreherbicidal compounds (b) in a weight ratio of 1:0.1 to 1:40.
 8. Aherbicidal mixture as claimed in claim 7, comprising a sulfonylurea (a)of the formula I and one or more herbicidal compounds (b) in a weightratio of 1:0.2 to 1:20.
 9. A herbicidal composition comprising aherbicidally active amount of a sulfonylurea (a) of the formula I asclaimed in any of claims 1 to 4, a synergistically active amount of atleast one herbicidal compound (b) as claimed in any of claims 1, 5 or 6,at least one liquid and/or solid carrier and, if desired, at least oneadjuvant.
 10. A herbicidal composition as claimed in claim 9, whichcomprises the sulfonylurea (a) of the formula I and one or moreherbicidal compounds (b) in a weight ratio of 1:0.1 to 1:40.
 11. Aherbicidal composition as claimed in claim 9 or 10, which comprises thesulfonylurea (a) of the formula I and one or more herbicidal compounds(b) in a weight ratio of 1:0.2 to 1:20.
 12. A method of controllingundesirable vegetation, which comprises applying a sulfonylurea (a) ofthe formula I as set forth in any of claims 1 to 4 and one or moreherbicidal compounds (b) as set forth in claim 1 before, during and/orafter the emergence of undesirable plants, either simultaneously or insuccession.
 13. A method of controlling undesirable vegetation, whichcomprises treating the leaves of the crop plants and of the undesirableplants with a sulfonylurea (a) of the formula I as set forth in any ofclaims 1 to 4 and one or more compounds (b) as set forth in claim 1,either simultaneously or in succession.